Use of improved cyan pigments in electrophotographic toners and developers, powder coatings and inkjet inks

ABSTRACT

The present invention relates to the use of a CuPc composition consisting essentially of CuPc, e.g., C.I. Pigment Blue 15:3, and a hydroxymethylphthalimido CuPc, as a colorant in electrophotographic toners and developers, powders and powder coating materials, electret materials, inkjet inks, and color filters, wherein the phthalocyanines have a particle morphology with an average length-to-width ratio of more than 2.5:1.

BACKGROUND OF THE INVENTION

[0001] The present invention relates to the use of a certain copperphthalocyanine composition in electrophotographic toners and developers,powder coating materials and inkjet inks.

[0002] In electrophotographic recording techniques a “latent chargeimage” is produced on a photoconductor. This latent charge image isdeveloped by applying an electrostatically charged toner which is thentransferred, for example, to paper, textiles, foils or plastic and isfixed by means, for example, of pressure, radiation, heat, or the actionof a solvent. Typical toners are one- or two-component powder toners(also called one- or two-component developers); furthermore specialtoners are employed, examples being magnetic or liquid toners, latextoners, polymerization toners and microencapsulated toners based on wax,for example.

[0003] One measure of the quality of a toner is its specific charge q/m(charge per unit mass). In addition to the sign and level of theelectrostatic charge, the rapid attainment of the desired charge leveland the constancy of this charge over a prolonged activation period, inparticular, is a decisive quality criterion. Moreover, the insensitivityof the toner to climatic effects such as temperature and atmospherichumidity is another important criterion for its suitability.

[0004] Both positively and negatively chargeable toners are used inphotocopiers, laser printers, LED (light emitting diode), LCS (liquidcrystal shutter) printers or other digital printers based onelectrophotography, depending on the type of process and type ofequipment.

[0005] In order to obtain electrophotographic toners or developers witheither a positive or a negative charge it is common to add chargecontrol agents. As the color-imparting component in color toners, use istypically made of organic color pigments. As compared with dyes, colorpigments have considerable advantages on account of their insolubilityin the application medium, such as improved thermal stability andlightfastness, for example.

[0006] On the basis of the principle of subtractive color mixing it ispossible, with the aid of the three primary colors yellow, cyan andmagenta, to reproduce the entire spectrum of colors visible to the humaneye. Exact color reproduction is only possible if the particular primarycolor satisfies the precisely defined color requirements. If this is notthe case, some shades cannot be reproduced and the color contrast isinadequate.

[0007] In the case of full color toners, the three toners yellow, cyanand magenta must not only meet the precisely defined color requirementsbut must also be matched exactly to one another in their triboelectricproperties, since they are transferred one after another in the samedevice.

[0008] 6- and 7-color systems are likewise known. The base colors arered, green, blue, cyan, magenta, yellow and black. it is also possibleto produce full color prints by the Pantone Hexachrome® system with thecolors cyan, magenta, yellow, black, orange and green.

[0009] It is known that colorants may have a long-term effect on thetriboelectric charging of toners. As a result, it is normally notpossible simply to add the colorants to a toner base formulation onceprepared. It may instead be necessary to prepare a specific formulationfor each colorant, with the nature and amount of the required chargecontrol agent being tailored specifically. This approach is,correspondingly, laborious and in the case of color toners for processcolor is just another difficulty to add to those already describedabove.

[0010] Furthermore, it is important for practical use that the colorantspossess high thermal stability and good dispersibility. Typicaltemperatures for incorporation of colorants into the toner resins arebetween 100° C. and 200° C. when using compounders or extruders.Accordingly, a thermal stability of 200° C., or even better 250° C., isa great advantage. It is also important that the thermal stability ismaintained over a prolonged period (about 30 minutes) and in differentbinder systems. Typical toner binders are resins formed by additionpolymerization, polyaddition and polycondensation, such as styrene,styrene-acrylate, styrene-butadiene, acrylate, polyester andphenol-epoxy resins, polysulfones and polyurethanes, individually or incombination.

[0011] Fundamentally there is a need for color pigments possessing avery high degree of transparency, good dispersibility and a low inherentelectrostatic effect: as far as possible a neutral inherenttriboelectric effect. Neutral inherent triboelectric effect means thatthe pigment has very little or no effect on the inherent electrostaticcharging of the resin and readily follows a defined charge establishedby means, for example, of charge control agents.

[0012] Transparency is of great importance since, in the case of fullcolor copies or in printing, the colors yellow, cyan and magenta arecopied or printed over one another, the sequence of colors depending onthe device. Consequently, if an overlying color is not sufficientlytransparent, then the underlying color is unable to show through to asufficient extent and the color reproduction is distorted. In the caseof copying or printing on sheets for overhead projection use,transparency is even more important, since in this case a lack oftransparency even in just one color makes the whole of the projectedimage gray.

[0013] The cyan shade, furthermore, is of great importance since it isused both in four-color printing and in 6- or 7-color printing.

SUMMARY OF THE INVENTION

[0014] The object of the present invention is to provide an improvedcyan pigment satisfying the above requirements for use inelectrophotographic toners and developers, powder coating materials,inkjet inks, color filters, and electret fibers.

[0015] This object has surprisingly been achieved by the use of thecopper phthalocyanine composition defined hereinbelow.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The present invention provides for the use of a copperphthalocyanine composition consisting essentially of a compound of theformula (I)

[0017] and of a compound of the formula (II)

[0018] as a colorant in electrophotographic toners and developers,powders and powder coating materials, electret materials, inkjet inks,and color filters, wherein the compounds of the formulae (I) and (II)have a particle morphology with an average length-to-width ratio of morethan 2.5:1, preferably from 3:1 to 6:1.

[0019] The relative proportions of the compound of the formula (I) tothe compound of the formula (II) can fluctuate within wide limits; forexample, from 0.1:99.9% by weight to 99.9:0.1% by weight. Preference isgiven to compositions of from 80 to 99.5% by weight of the compound ofthe formula (I) and from 0.5 to 20% by weight of the compound of theformula (II). Particular preference is given to compositions of from 90to 99% by weight of the compound of the formula (I) and from 1 to 10% byweight of the compound of the formula (II).

[0020] The compound of the formula (I) is known per se (DE-A-2 432 564)and is in commerce under the designation C.I. Pigment Blue 15. Theβ-modification is preferred, being known under the names C.I. PigmentBlue 15:3 and 15:4. Also suitable in principle, however, are theα-modification (C.I. Pigment Blue 15:1 and 15:2, from 0.5 to 1 Cl) andthe ,-modification (C.I. Pigment Blue 15:6).

[0021] The compound of the formula (II) is known per se and can beprepared in analogy to EP-A-0 508 704 by reacting theN-methylol-phthalimide with a phthalocyanine.

[0022] Conventional C.I. Pigment Blue 15, especially 15:3, possesses avery pronounced intrinsic triboelectric effect (e.g., U. Schlosser etal., Society of Imaging Science and Technology, 11th Congress onAdvances in Non-impact Printing Technology, Hilton Head, S.C., Oct.29-Nov. 11, 1995, Proceedings pp 110-112) which can be overcome onlywith great effort and in many cases only partly by means, for example,of adding charge control agents, which is very expensive.

[0023] It is novel and surprising that the phthalocyanine compositionused in accordance with the invention and having the stated particlemorphology possesses a very stable and neutral intrinsic triboelectriceffect and exhibits a significant improvement in respect of transparencyand dispersibility. The intrinsic triboelectric effect is the influenceof the colorant on the electrostatic charging of the binder. The normalaim is that the colorant should not alter the charging behavior of thebinder. Ideally, irrespective of the-addition of colorant, the binderhas the same charge per mass after the same activation time. The factthat a needle-shaped (acicular) particle morphology in the copperphthalocyanine composition of the invention leads to a stable andneutral intrinsic triboelectric effect was very surprising, since it isknown from EP-A-0 813 117 that the colorant used therein has anintrinsic triboelectric effect which is more stable and neutral the lessthe extent to which the pigment particles are needle-shaped, i.e., thegreater the extent to which the pigment particles are cube-shaped—inother words, precisely the opposite of the present case. It was furthersurprising that the copper phthalocyanine composition of the inventiondespite its needle-shaped particle morphology has high flocculationstability, ready dispersibility, in aqueous and nonaqueous media, andhigh color strength and luster. Ease of dispersibility is of importancenot only for toners, powder coating materials and electret materials butalso, in particular, for inkjet inks, since in this case the pigmentdispersion must be extremely fine in order not to block the very fineprinter nozzles.

[0024] Furthermore, the copper phthalocyanine composition thus preparedhas a high negative particle surface charge: for example, in the rangefrom −60 to −300 mV/mg, in particular from −60 to −120 mV/mg.

[0025] The phthalocyanine composition of the invention can be preparedby finely dividing crude copper phthalocyanine with a suitable grindingapparatus—for example, on a ballmill or beadmill—subjecting the finelydivided copper phthalocyanine to a solvent finish in aqueous-organic ororganic medium at a temperature of from 20 to 200° C. for a period oftime permitting crystal growth, e.g., at least ½ hour, preferably from 2to 10 hours, and then adding the phthalimidomethylene CuPc. Examples ofsuitable organic media are alcohols, such as n- or i-butanol, ketones,such as methyl ethyl ketone, methyl isobutyl ketone or diethyl ketoneand carboxamides, such as DMF or dimethylacetamide.

[0026] As well as in electrophotographic toners and developers, thecopper phthalocyanine composition can also be used as colorant inpowders and coating materials, especially in triboelectrically orelectrokinetically sprayed powder coating materials as used to coat thesurfaces of articles made, for example, from metal, wood, textilematerial, paper or rubber. The powder coating or powder obtains itselectrostatic charge in general by one of the two following methods:

[0027] a) in the case of the corona method, the powder coating materialor powder is guided past a charged corona and is charged in the process;

[0028] b) in the case of the triboelectric or electrokinetic method, theprinciple of frictional electricity is utilized.

[0029] Typical powder coating resins employed are epoxy resins,carboxyl- and hydroxyl-containing polyester resins, polyurethane resinsand acrylic resins together with the customary hardeners. Resincombinations are also used. For example, epoxy resins are frequentlyemployed in combination with carboxyl- and hydroxyl-containing polyesterresins.

[0030] Furthermore, the improved triboelectric behavior of the colorantmay result in an improvement in the electret properties in the case ofcolored (pigmented) electret materials, typical electret materials beingbased on polyolefins, halogenated polyolefins, polyacrylates,polyacrylonitriles, polystyrenes or fluoropolymers, examples beingpolyethylene, polypropylene, polytetrafluoroethylene and perfluorinatedethylene and propylene, or on polyesters, polycarbonates, polyamides,polyimides, polyether ketones, on polyarylene sulfides, especiallypolyphenylene sulfides, on polyacetals, cellulose esters, polyalkyleneterephthalates, and mixtures thereof. Electret materials have numerousfields of use and may acquire their charge through corona charging ortriboelectric charging (ref.: G. M. Sessler, “Electrets”, Topics inApplied Physics, Vol. 33, Springer Verlag, New York, Heidelberg, 2ndEd., 1987).

[0031] Furthermore, the improved triboelectric influence of the colorantmay result in improved separation characteristics of colored (pigmented)polymers which are separated by electrostatic methods (Y. Higashiyau, J.of Electrostatics, 30, pages 203-212, 1993). Accordingly, the inherenttriboelectric effect of pigments is important for the mass coloring ofplastics as well. The inherent triboelectric effect is also significantin process or processing steps which involve intense frictional contact,examples being spinning processes, film-drawing processes or othershaping processes.

[0032] Furthermore, the phthalocyanine composition is also suitable as acolorant for color filters, both for subtractive and for additive colorgeneration (P. Gregory “Topics in Applied Chemistry: High TechnologyApplication of Organic Colorants” Plenum Press, New York 1991, pp.15-25).

[0033] A task frequently encountered in connection withelectrophotographic color toners, powder coating materials or inkjetinks is to shade the hue and adapt it to the requirements of thespecific application. Particularly appropriate for this purpose arefurther organic color pigments, inorganic pigments, and dyes. Furtherorganic color pigments can be used in mixtures with the copperphthalocyanine composition in concentrations between 0.01 and 50% byweight, preferably between 0.1 and 25% by weight and, with particularpreference, between 0.1% and 15% by weight, based on the copperphthalocyanine composition. The further organic color pigments can befrom the group of the azo pigments or polycyclic pigments.

[0034] Preferred blue and/or green pigments for shading are therespective other copper phthalocyanines, such as C.I. Pigment Blue 15,15:1, 15:2, 15:3, 15:4, 15:6, P. Blue 16 (metal-free phthalocyanine), orphthalocyanines with aluminum, nickel, iron or vanadium as the centralatom, and also triarylcarbonium pigments, such as Pigment Blue 1, 2, 9,10,14, 62 and Pigment Green 1, 4 and 45. Mixtures of one or morecomponents are likewise suitable. Relatively large steps in hue arepossible, for example, using orange pigments such as P.O. 5, 62, 36, 34,13, 43 and 71; yellow pigments such as P.Y. 12, 13, 17, 83, 93, 122,155, 180, 174, 185 and 97; red pigments such as P.R. 48, 57, 122, 146,184, 186, 202, 207, 209, 254, 255, 270 and 272; or violet pigments suchas P.V. 1 and 19. The mixtures can be prepared in the form of powders,by mixing presscakes, spray-dried presscakes or masterbatches and bydispersion (extrusion, kneading, roll-mill processes, bead mills,Ultra-Turrax) in the presence of a carrier material in solid or liquidform (aqueous and nonaqueous inks) and by flushing in the presence of acarrier material. If the colorant is used with high proportions of wateror solvent

[0035] (>5%), then mixing can also take place at elevated temperatureswith vacuum assistance.

[0036] Particularly appropriate for increasing the brightness but alsofor shading the hue are mixtures with organic dyes. Preferred such dyesare water-soluble dyes, such as direct, reactive and acid dyes, and alsosolvent-soluble dyes, such as solvent dyes, disperse dyes and vat dyes.Specific examples that may be mentioned are C.I. Reactive Yellow 37,Acid Yellow 23, Reactive Red 23, 180, Acid Red 52, Reactive Blue 19, 21,Acid Blue 9, Direct Blue 199, Solvent Yellow 14, 16, 25, 56, 62, 64, 79,81, 82, 83, 83:1, 93, 98, 133, 162, 174, Solvent Red 8,19, 24, 49, 89,90, 91, 92, 109, 118, 119, 122, 124, 127, 135, 160, 195, 212, 215,Solvent Blue 44, 45, Solvent Orange 41,60, 63, Disperse Yellow 64, VatRed 41, and Solvent Black 45, 27.

[0037] It is also possible to use dyes and pigments having fluorescentproperties, such as ®Luminols (Riedel-de Haen), in concentrations offrom 0.0001 to 10% by weight, preferably from 0.001 to 5% by weight and,with very particular preference, between 0.01 and 1%, based on thephthalocyanine composition, in order, for example, to produceanticounterfeit toners.

[0038] Inorganic pigments, such as TiO₂ or BaSO₄, are used in mixturesfor lightening. Also suitable are mixtures with effect pigments, such aspearl luster pigments, Fe₂O₃ pigments (®Paliochromes) and pigments basedon cholesteric polymers, for example, which give different perceivedcolors depending on the viewing angle.

[0039] The copper phthalocyanine composition employed in accordance withthe invention can also be combined with charge control agents, providingeither positive or negative control, in order to achieve definedcharging performance. The simultaneous use of positive and negativecharge control agents is a further option.

[0040] Examples of suitable charge control agents are:triphenylmethanes; ammonium and immonium compounds; iminium compounds;fluorinated ammonium and fluorinated immonium compounds; biscationicacid amides; polymeric ammonium compounds; diallylammonium compounds;aryl sulfide derivatives; phenol derivatives; phosphonium compounds andfluorinated phosphonium compounds; calix(n)arenes; cyclically linkedoligosaccharides (cyclodextrins) and their derivatives, especially boronester derivatives, interpolyelectrolyte complexes (IPECs); polyestersalts; metal complex compounds, especially carboxylate-metal,salicylate-metal and salicylate-nonmetal complexes, aluminum-azocomplexes, α-hydroxycarboxylic acid-metal and -nonmetal complexes; boroncomplexes of 1,2-dihyd roxyaromatics, 1,2-d ihydroxyaliphatics or2-hydroxy-1-carboxyaromatics; benzimidazolones; and azines, thiazines oroxazines which are listed in the Colour Index as Pigments, Solvent Dyes,Basic Dyes or Acid Dyes.

[0041] Examples of charge control agents which can be combinedindividually or in combination with one another with the phthalocyaninecomposition of the invention are:

[0042] triarylmethane derivatives such as, for example:

[0043] Colour Index Pigment Blue 1, 1:2, 2, 3, 8, 9, 9:1, 10, 10:1, 11,12, 14, 18, 19, 24, 53, 56, 57, 58, 59, 61, 62, 67 or, for example,Colour Index Solvent Blue 2, 3, 4, 5, 6, 23, 43, 54, 66, 71, 72, 81,124, 125, and also the triarylmethane compounds listed in the ColourIndex under Acid Blue and Basic Dye, provided they are suitable in termsof their thermal stability and processing properties, such as, forexample, Colour Index Basic Blue 1, 2, 5, 7, 8, 11, 15, 18, 20, 23, 26,36, 55, 56, 77, 81, 83, 88, 89, Colour Index Basic Green 1, 3, 4, 9, 10,with Colour Index Solvent Blue 125, 66 and 124 in turn possessingspecial suitability. Colour Index Solvent Blue 124, in the form of itshighly crystalline sulfate or of thetrichlorotriphenylmethyltetrachloroaluminate, is particularly suitable.Metal complexes bearing the CAS Numbers 84179-66-8 (chromium azocomplex), 115706-73-5 (iron azo complex), 31714-55-3 (chromium azocomplex), 84030-55-7 (chromium salicylate complex), 42405-40-3 (chromiumsalicylate complex) and also the quaternary ammonium compound CAS No.116810-46-9 and also aluminum azo complex dyes, metal carboxylates andsulfonates.

[0044] Examples of charge control agents of the triphenylmethane seriesthat are highly suitable for the production of electret fibers are thecompounds described in DE-A-1 919 724 and DE-A-1 644 619.

[0045] Of particular interest are triphenylmethanes as described in U.S.Pat. No. 5,051,585, especially those of the formula (2)

[0046] in which R¹ and R³ are phenylamino groups, R² is anm-methylphenylamino group, and the radicals R⁴ to R¹⁰ are all hydrogen.

[0047] Also suitable are ammonium and immonium compounds as described inU.S. Pat. No. 5,015,676, and fluorinated ammonium and immonium compoundsas described in U.S. Pat. No. 5,069,994, especially those of the formula(3)

[0048] in which

[0049] R¹³ is perfluorinated alkyl of 5 to 11 carbon atoms,

[0050] R²³, R³³ and R⁴³ are identical or different and are alkyl of 1 to5, preferably 1 to 2, carbon atoms, and

[0051] Y⁻ is a stoichiometric equivalent of an anion, preferably of atetrafluoroborate or tetraphenylborate anion.

[0052] Also suitable are biscationic acid amides, as described in WO91/10172.

[0053] Further suitable compounds are diallylammonium compounds asdescribed in DE-A-4,142,541 and also the polymeric ammonium compoundsobtainable therefrom of the formula (6), as described in DE-A-4 029 652or DE-A-4 103 610

[0054] in which n has a value corresponding to molecular weights of from5000 to 500,000 g/mol, preferably molecular weights of from 40,000 to400,000 g/mol.

[0055] Also suitable are aryl sulfide derivatives as described in DE-A-4031 705, especially those of the formula (7)

[0056] in which

[0057] R¹⁷, R²⁷, R³⁷ and R⁴⁷ are identical or different alkyl groups of1 to 5, preferably 2 or 3, carbon atoms, and

[0058] R⁵⁷ is one of the divalent radicals —S—, —S—S—, —SO—and —SO₂.

[0059] For example, R¹⁷ to R⁴⁷ are propyl groups and R⁵⁷ is the group—S—S—.

[0060] Also suitable are phenol derivatives as described in EP-A-0 258651, especially those of the formula (8)

[0061] in which

[0062] R¹⁸ and R³⁸ are alkyl or alkenyl groups of 1 to 5, preferably 1to 3, carbon atoms and R²⁸ and R⁴⁸ are hydrogen or alkyl of 1 to 3carbon atoms, preferably methyl.

[0063] Also suitable are phosphonium compounds and fluorinatedphosphonium compounds, as described in U.S. Pat. No. 5,021,473 and inU.S. Pat. No. 5,147,748.

[0064] Other suitable compounds include calix(n)arenes, as described inEP-A-0 385 580, EP-A-0 516 434 and in Angew. Chemie (1993), 195, 1258.

[0065] Further suitable compounds are metal complex compounds, such aschromium-, cobalt-, iron-, zinc- or aluminum-azo complexes or chromium-,cobalt-, iron-, zinc- or aluminum-salicylic or boric acid complexes ofthe formula (14)

[0066] in which

[0067] M* is a divalent central metal atom, preferably a chromium,aluminum, iron, boron or zinc atom,

[0068] R¹¹⁴ and R²¹⁴ are identical or different straight-chain orbranched alkyl groups of 1 to 8, preferably 3 to 6, carbon atoms, anexample being tert-butyl.

[0069] Also suitable are benzimidazolones as described in EP-A-0 347695.

[0070] Further suitable compounds are cyclically linked oligosaccharidesas described in DE-A4 418 842.

[0071] Further suitable compounds are polymer salts, as described inDE-A-4 332 170, especially the product described in Example 1 thereof.

[0072] Also suitable are cyclooligosaccharide compounds, as aredescribed, for example, in DE-A-1 971 1260, which are obtainable byreacting a cyclodextrin or cyclodextrin derivative with a compound ofthe formula

[0073] in which R¹ and R² are alkyl, preferably C₁-C₄-alkyl.

[0074] Also suitable are interpolyelectrolyte complexes as aredescribed, for example, in DE-A-197 32 995. Particularly suitable suchcompounds are those featuring a molar ratio of polymeric cationic topolymeric anionic groups of from 0.9:1.1 to 1.1:0.9.

[0075] Further suitable compounds, especially for use in liquid toners(Handbook of Imaging Materials, 1991, Marcel Dekker, Inc., Chapter 6,Liquid Toner Technology), are surface-active ionic compounds and whatare known as metal soaps.

[0076] Particularly suitable are alkylated arylsulfonates, such asbarium petronates, calcium petronates, bariumdinonylnaphthalenesulfonates (basic and neutral), calciumdinonylsulfonate or sodium dodecylbenzenesulfonate, andpolyisobutylenesuccinimides (Chevron's ®Oloa 1200). Soya lecithin andN-vinylpyrrolidone polymers are also suitable. Also suitable are sodiumsalts of phosphated mono- and diglycerides of saturated and unsaturatedsubstituents, AB diblock copolymers of A: polymers of2-(N,N)-dimethylaminoethyl methacrylate quaternized with methylp-toluenesulfonate, and B: poly-2-ethylhexyl methacrylate.

[0077] Also suitable, especially in liquid toners, are divalent andtrivalent carboxylates, especially aluminum tristearate, bariumstearate, chromium stearate, magnesium octoate, calcium stearate, ironnaphthalite and zinc naphthalite.

[0078] Suitability extends to chelating charge control agents, asdescribed in EP 0 636 945 A1, metallic (ionic) compounds, as describedin EP 0 778 501 A1, phosphate metal salts, as described in JA 9(1997)-106107, azines of the following Colour Index Numbers: C.I.Solvent Black 5, 5:1, 5:2, 7, 31 and 50; C.I. Pigment Black 1, C.i.Basic Red 2 and C.I. Basic Black 1 and 2.

[0079] The combination of phthalocyanine composition of the inventionand charge control agents can be effected by means of physical mixing ofthe respective powders, presscakes or masterbatches, or by appropriateapplication to the surface of the pigment (pigment coating). Bothcomponents can also advantageously be added in the case ofpolymerization toners, for which the binder is polymerized in thepresence of the copper phthalocyanine composition of the invention and,if appropriate, of the charge control agent, or can be used in thepreparation of liquid toners in high-boiling inert solvents, such ashydrocarbons.

[0080] The copper phthalocyanine composition of the invention is alsosuitable for aqueous-based electrocoagulation toners.

[0081] The invention therefore also provides an electrophotographictoner or developer comprising a toner binder, from 0.1 to 60% by weight,preferably from 0.5 to 20% by weight, of shaded or unshadedphthalocyanine composition, and from 0 to 20% by weight, preferably from0.1 to 5% by weight, based in each case on the overall weight of thetoner or developer, of a charge control agent from the class of thetriphenylmethanes, ammonium and immonium compounds; fluorinated ammoniumand immonium compounds; biscationic acid amides; polymeric ammoniumcompounds; diallylammonium compounds; aryl sulfide derivatives; phenolderivatives; phosphonium compounds and fluorinated phosphoniumcompounds; calix(n)arenes; cyclodextrins; polyester salts; metal complexcompounds; cyclooligosaccharide-boron complexes, interpolyelectrolytecomplexes; benzimidazolones; azines, thiazines or oxazines.

[0082] It is also possible to add further components to the toner, suchas waxes, which may be of animal, vegetable or mineral origin, syntheticwaxes, or mixtures thereof. Waxes are understood to be substances whichare kneadable at 20° C., ranging from firm to hard and fragile, fromcoarse to finely crystalline, and from translucent to opaque, but notgrasslike. In addition, a light stabilizer can be added to the toner.Subsequently, free flow agents, such as TiO₂ or highly disperse silica,can also be added to the toner.

[0083] The invention additionally provides a powder or powder coatingmaterial comprising an acrylic resin or polyester resin containingepoxy, carboxyl or hydroxyl groups, or a combination of such resins,from 0.1 to 60% by weight, preferably from 0.5 to 20% by weight, ofshaded or unshaded phthalocyanine composition, and from 0 to 20% byweight, preferably from 0.1 to 5% by weight, based in each case on theoverall weight of the powder or powder coating material, of a chargecontrol agent selected from the preferred compounds and classesmentioned above for electrophotographic toners.

[0084] The phthalocyanine composition used in accordance with theinvention is judiciously incorporated homogeneously, for example byextrusion or kneading, or added during the polymerization of the binder,in a concentration of from 0.1 to 60% by weight, preferably from 0.5 to20% by weight and, with particular preference, from 0.1 to 5.0% byweight, based on the overall mixture, into the binder of the respectivetoner (liquid or dry), developer, powder coating material, electretmaterial or polymer for electrostatic separation. In this context, thecopper phthalocyanine composition and, if appropriate, theabovementioned charge control agent can also be added in the form ofdried and ground powders, dispersions or suspensions in, for example,organic and/or inorganic solvents, presscakes (which can be used, forexample, for the flush process), spray-dried presscakes, masterbatches,preparations, made-up pastes, and as compounds applied to suitablecarriers, examples being kieselguhr, TiO₂, Al₂O₃, from aqueous ornonaqueous solution, or in some other form. The phthalocyanine contentin the presscake and masterbatch is usually between 5 and 70% by weight,preferably between 20 and 50% by weight. Furthermore, the phthalocyaninecomposition can also be used as a highly concentrated presscake,especially as a spray-dried presscake, in which case the phthalocyaninecontent is between 25 and 95% by weight, preferably between 50 and 90%by weight.

[0085] The level of the electrostatic charge of the electrophotographictoners or of the powder coatings into which the pigment of the inventionis homogeneously incorporated cannot be predicted and is measured onstandard test systems under identical conditions (identical dispersiontimes, identical particle size distribution, identical particlemorphology) at approximately 20° C. and 50% relative atmospherichumidity. The electrostatic charging of the toner is carried out byfluidization with a carrier, i.e. a standardized friction partner (3parts by weight of toner per 97 parts by weight of carrier) on a bed ofrolls (150 revolutions per minute). Subsequently, the electrostaticcharging is measured on a customary qlm measurement setup.

[0086] The triboelectric spraying of the powders or powder coatingmaterials is carried out using a spraying apparatus with a standardspray pipe and a star-shaped inner rod at maximum powder throughput witha spray pressure of 3 bar. For this purpose, the article to be sprayedis suspended in a spray booth and is sprayed from a distance of about 20cm directly from the front, without any further movement of the sprayingapparatus. The charge of each sprayed powder is then measured using a“Device for measuring the triboelectric charge of powders” from Intec(Dortmund). To carry out the measurement, the antenna of the measuringdevice is held directly in the cloud of powder emerging from thespraying apparatus. The current strength resulting from theelectrostatic charge of powder coating material or powder is displayedin μA. The deposition rate is determined subsequently in % bydifferential weighing of the sprayed and of the deposited powder coatingmaterial.

[0087] The transparency and color strength in toner binder systems isinvestigated as follows: 30 parts by weight of the pigmented test tonerare stirred with a dissolver (5 minutes at 5000 rpm) into 70 parts byweight of a base varnish (consisting of 15 parts by weight of therespective toner resin and 85 parts by weight of ethyl acetate).

[0088] The test toner varnish produced in this way is knife-coated ontosuitable paper (e.g., letterpress paper), using a manual coater, againsta standard pigmented varnish produced in the same way. A suitable sizefor the coater bar is, for example, K bar N 3 (=24 μm coat thickness).To allow better determination of transparency, the paper has printed onit a black bar, and the transparency and color strength differences interms of dL values are determined in accordance with DIN 55 988 orevaluated in accordance with the test procedure from Pigments Marketing,Clariant GmbH “Visuelle und Farbmetrische Bewertung von Pigmenten”[Visual and calorimetric evaluation of pigments] version 3, 1996 (No.1/1).

[0089] It has also been found that the copper phthalocyanine compositionis suitable as a colorant in aqueous (including microemulsion inks) andnonaqueous (“solvent-based”) inkjet inks, and in those inks whichoperate in accordance with the hot-melt technique.

[0090] Microemulsion inks are based on organic solvents, water and, ifdesired, an additional hydrotropic substance (interface mediator).Nonaqueous inks contain essentially organic solvents and, if desired, ahydrotropic substance.

[0091] The present invention additionally provides inkjet recordingliquids which comprise the phthalocyanine composition.

[0092] The finished recording liquids generally include from 0.5 to 15%by weight, preferably from 1.5 to 8% by weight, of the copperphthalocyanine composition, based on the overall weight of the recordingliquid.

[0093] Microemulsion inks consist essentially of from 0.5 to 15% byweight, preferably from 1.5 to 8% by weight of the phthalocyaninecomposition, from 5 to 99% by weight of water and from 0.5 to 94.5% byweight of organic solvent and/or hydrotropic compound.

[0094] “Solvent based” inkjet inks consist essentially of from 0.5 to15% by weight of the phthalocyanine composition and from 85 to 94.5% byweight of an organic solvent and/or hydrotropic compound. Carriermaterials for “solvent based” inkjet inks can be polyolefins, naturalrubber and synthetic rubber, polyvinyl chloride, vinyl chloride/vinylacetate copolymers, polyvinyl butyrates, wax/latex systems orcombinations thereof which are soluble in the “solvent”.

[0095] Hot-melt inks are based predominantly on organic compounds, suchas waxes, fatty acids, fatty alcohols or sulfonamides, which are solidat room temperature and liquefy when heated, the preferred melting rangelying between about 60° C. and about 140° C.

[0096] The invention also provides a hot-melt inkjet ink consistingessentially of from 20 to 90% by weight of wax and from 1 to 10% byweight of the phthalocyanine composition, unshaded or shaded by furthercolorants, from 0 to 20% by weight of an additional polymer (as“colorant dissolver”), from 0 to 5% by weight of dispersing auxiliaries,from 0 to 20% by weight of viscosity modifiers, from 0 to 20% by weightof plasticizers, from 0 to 10% by weight of tack additive, from 0 to 10%by weight of transparency stabilizer (prevents, e.g., crystallization ofwaxes), and from 0 to 2% by weight of antioxidant.

[0097] The solvents present in the recording liquids described above cancomprise an organic solvent or a mixture of such solvents. Examples ofsuitable solvents are mono- or polyhydric alcohols, their ethers andesters, e.g., alkanols, especially those of 1 to 4 carbon atoms, such asmethanol, ethanol, propanol, isopropanol, butanol and isobutanol;dihydric or trihydric alcohols, especially those of 2 to 5 carbon atoms,examples being ethylene glycol, propylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol,glycerol, diethylene glycol, dipropylene glycol, triethylene glycol,polyethylene glycol, tripropylene glycol, polypropylene glycol; loweralkyl ethers of polyhydric alcohols, such as, for example, ethyleneglycol monomethyl, monoethyl or monobutyl ether, triethylene glycolmonomethyl or monoethyl ether; ketones and ketone alcohols such as, forexample, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutylketone, methyl pentyl ketone, cyclopentanone, cyclohexanone anddiacetone alcohol; amides, such as dimethylformamide, dimethylacetamide,N-methylpyrrolidone, toluene and n-hexane, for example.

[0098] Water used to prepare the recording liquids is used preferably inthe form of distilled or deionized water.

[0099] Hydrotropic compounds, which may also act as solvents, includefor example formamide, urea, tetramethylurea, ε-caprolactam, ethyleneglycol, diethylene glycol, triethylene glycol, polyethylene glycol,butyl glycol, methyl-Cellosolve, glycerol,

[0100] N-methylpyrrolidone, 1,3-diethyl-2-imidazolidinone, thiodiglycol,sodium benzenesulfonate, Na xylenesulfonate, Na toluenesulfonate, sodiumcumenesulfonate, Na dodecylsulfonate, Na benzoate, Na salicylate orsodium butyl monoglycol sulfate.

[0101] The recording liquids of the invention may also include othercustomary additives, examples being preservatives, cationic, anionic ornonionic surface-active substances (surfactants and wetting agents), andalso viscosity regulators, e.g., polyvinyl alcohol, cellulosederivatives, or water-soluble natural or synthetic resins as filmformers and/or binders for increasing the adhesive strength and abrasionresistance.

[0102] Amines, such as ethanolamine, diethanolamine, triethanolamine,N,N-dimethylethanolamine or diisopropylamine, for example, serveprimarily to increase the pH of the recording liquid. They are normallypresent in the recording liquid in a proportion of from 0 to 10%,preferably from 0.5 to 5%, by weight.

[0103] The inkjet inks of the invention can be prepared by dispersingthe copper phthalocyanine composition—in the form of a powder, anaqueous or nonaqueous preparation, a suspension or a presscake—into themicroemulsion medium or into the aqueous or nonaqueous medium or intothe wax for preparing a hot-melt inkjet ink. The presscake can also be ahighly concentrated presscake, especially a spray-dried presscake.

[0104] In addition to printing on paper, natural and synthetic fibermaterials, films or plastics, inkjet inks can also be used on glass,ceramic, concrete and the like.

EXAMPLES

[0105] In the examples below, parts and percentages are by weight. CuPcdenotes copper phthalocyanine.

Synthesis Example 1

[0106] 1.1 Preparation of Crude Copper Phthalocyanine

[0107] The synthesis of C.I. Pigment Blue 15:3 (copper phthalocyanine, βmodification) takes place, for example, as decribed in DE-A-24 32 564,Example 1. The crude copper phthalocyanine produced in this way issubsequently suspended in water and ground in a laboratory ball mill for24 hours.

[0108] 1.2 Preparation of the Phthalimidomethyl-CuPc Additive

[0109] In a 1 liter reaction vessel, 216 ml of water, 90 g of formalin(35% strength) and 120 g of phthalimide are combined with stirring atroom temperature and subsequently heated to 100° C. A clear solution isformed, which is cooled. The reaction product which precipitates isfiltered off, washed and dried.

[0110] Yield (dry): 136 g of hydroxymethylphthalimide.

[0111] In a 1 liter reaction vessel, 32 g of crude copper phthalocyaninefrom Synthesis Example 1.1 are added slowly with stirring to 240 ml of98% strength sulfuric acid at 35° C.

[0112] Subsequently, 40 g of the hydroxymethylphthalimide are addedslowly. The reaction mixture is heated to about 80° C., then cooled toroom temperature and poured into an ice-water mixture. The precipitateis filtered and washed.

[0113] Yield: 260 g of presscake (20% solids content) ofphthalimidomethyl-CuPc.

[0114] 1.3 Solvent Finish

[0115] In a 500 ml reaction vessel, 50 g of the crude CuPc describedunder 1.1 are stirred at room temperature into 100 ml of water. Then 100ml of methyl ethyl ketone are added and the mixture is boiled at reflux(74° C.) for 2 hours with stirring. The solvent is distilled off underatmospheric pressure (about 80° C.) with the simultaneous slow additionof 100 ml of H₂O. Subsequently, at about 80° C., 6.25 g of thephthalimidomethyl-CuPc presscake described under 1.2 are added. Thereaction mixture thus obtained is stirred for several hours at 60-80° C.The end product is filtered off, washed, filtered off with suction andsubsequently dried and ground.

[0116] Yield: 50 g of blue pulverulent copper phthalocyaninecomposition.

[0117] Product characterization: pH 6.5 Residual moisture content(baking flask) 0.3% Residual salt content: 70 μS/cm BET surface area:61.3 m²/g Particle size: d₂₅: 0.08 μm  d₅₀: 0.1 μm  d₇₅: 0.13 μmParticle morphology (length-to-width ratio) Total sample:  3.06:1 Finefraction 2.87:1  Middle fraction 3.19:1  Coarse fraction 3.13:1

[0118] Particle size and particle morphology are determined by means ofan electron micrograph of the pigment powder. For this purpose thepigment is dispersed for 15 minutes in water and subsequently applied byspraying. The micrographs are taken at 13,000 and 29,000 timesmagnification.

[0119] Thermalstability: A DTA (differential thermoanalysis, 3° C./minheating rate, closed glass ampule) shows a thermalstability ofdistinctly more than 200° C.

[0120] X-ray diffraction diagram (CuK_(∀) radiation):

[0121] 2 theta (s=strong, m=moderate, w=weak): Width at half peak height2 Theta Intensity (relative intensity) (2 theta) 7.0 100%  0.28 9.2 76%0.28 10.5 14% 0.28 12.5 13% 0.26 18.2 17% 0.2 18.5 17% 0.2 21.4 12% 0.223.0 11% 0.22 23.8 40% 0.24 26.2 28% 0.26 28.0 15% 0.24 30.4 16% 0.25

[0122] Transparency

[0123] In a toner resin (bisphenol A based polyester) an improvedtransparency is measured (24 μm layer thickness), the pigmented testtoner being prepared as in Application Example 2.

[0124] Relative to the standard indicated in Synthesis Example 2(comparative), a transparency higher by 4-5 points is found afteradjusting for equal color strength.

[0125] Evaluation of the transparency differences in accordance withtest specification 1/1:1

trace, 2

somewhat; 3

markedly; 4

distinctly; 5

substantially; 6

significantly more transparent.

[0126] Color strength: Relative to the standard indicated in SynthesisExample 2, the pigment from Synthesis Example 1 is 10% stronger incolor.

[0127] Particle Surface Charge

[0128] The electrokinetic particle surface charge is determined asdescribed in Chimia 48 (1994) 516-517 and the literature cited therein.For a measured sample volume of 2 ml and a pigment concentration of 5g/l, the corresponding pigment particle surface charge is obtained inmV/mg, the measurements being taken in each case in the acid range, inthe alkaline range and at the intrinsic pH of the substance sample: pHmV/mg acidic (4.1) −60 intrinsic pH (6.5) −71 alkaline (10.0) −93

Synthesis Example 2 (Comparative Example)

[0129] The pigment used is ®Hostaperm Blue B2G (C.I. Pigment Blue 15:3,unsubstituted copper phthalocyanine) which is commonly used in numeroustoners and is prepared, for example, in accordance with DE-A-3 023 722.The CuPc additive was not added. Pigment characterization pH 6.4Residual moisture content (baking flask) 0.2% Residual salt content: 50μS/cm BET surface area: 50.2 m²/g Particle size: d₂₅: 0.07 μm  d₅₀: 0.09μm  d₇₅: 0.11 μm Particle morphology (length-to-width ratio) Totalsample:  2.67:1 Fine fraction 2.33:1  Middle fraction 2.62:1  Coarsefraction 2.96:1

Synthesis Example 3 (Comparative Example)

[0130] 20 g of the crude CuPc described under Synthesis Example 1.1 areintroduced into 300 ml of 66.5% strength sulfuric acid at 350C. Thesuspension is stirred at 350C for 2.5 hours and then poured into 320 mlof water. The mixture is heated to 80° C. and stirred at 80° C. for 1hour. It is then filtered and washed with water in order to extract thesulfuric acid.

[0131] The presscake is stirred together with water to form a readilystirrable suspension, and 10.7 g of 20% strength phthalimidomethyl-CuPcpresscake are added at room temperature. The mixture is then heated to135° C. under superatmospheric pressure and stirred at 135° C. for 7hours. The product is filtered at 60° C., washed, dried at 80° C. andpulverized: pH 6.5 Residual moisture content (baking flask) 0.3%Residual salt content: 70 μS/cm BET surface area: 49 m²/g Particle size:d₂₅: 0.08 μm  d₅₀: 0.1 μm  d₇₅: 0.17 μm Particle morphology(length-to-width ratio) Total sample:  1.62:1 Fine fraction2.07:1  Middle fraction 1.92:1  Coarse fraction 1.38:1

[0132] Application Examples for Toners

[0133] 5 parts of the respective colorant are incorporated homogeneouslyusing a kneading apparatus into 95 parts of a toner binder (polyesterresin based on bisphenol A, ®Almacryl T500) over the course of 30minutes. The product is then ground on a universal laboratory mill andclassified on a centrifugal classifier. The desired particle fraction(from 4 to 25 μm) is activated with a carrier consisting ofsilicone-coated ferrite particles of size 50 to 200 μm (bulk density2.75 g/cm³) (FBM 96-100; from Powder Tech.).

[0134] Measurement is carried out on a conventional q/m measurementsetup. A sieve having a mesh size of 25 μm is used to ensure that nocarrier is entrained when the toner is blown out. The measurements aremade at a relative atmospheric humidity of approximately 50%. As afunction of the activation period, the following q/m values [μC/g] aremeasured: Appli- cation Ex- Activation period / q/m in [μC/g] ampleToner system 5 min 10 min 30 min 2 h 24 h 1 (resin Polyester resin only,−20 −20 −17 −13  −8 line) no colorant 2 Polyester resin +5% −19 −12 −8 −6  −4 colorant from Synthesis Ex. 1 3 Polyester resin +5% −12 −9  −3 +2  +3 (com- colorant from para- Synthesis Ex. 2 tive) 4 Polyester resin+5% −18 −6  −3  −2  0 (com- colorant from para- Synthesis Ex. 3 tive

[0135] It is found that the toner containing the colorant of theinvention (Application Example 2) best follows the charging behavior ofthe resin line (Application Example 1).

Application Example 5

[0136] 5 parts of the colorant from Synthesis Example 1 and 1 part ofthe charge control agent of the formula

[0137] are incorporated into a polyester toner binder and subjected tomeasurement. As a function of the activation period, the following q/mvalues are measured: Activation period q/m [μC/g] 5 min −13 10 min −1130 min −10 2 h −9 23 h −9

[0138] Very good charging constancy over the entire activation period isfound.

Application Example 5

[0139] 5 parts of the colorant from Synthesis Example 1 and 1 part ofthe charge control agent of the formula

[0140] are incorporated into a styrene-acrylate toner binder andsubjected to measurement.

[0141] As a function of the activation period, the following q/m valuesare measured: Activation period q/m [μC/g]  5 min +2 10 min +3 30 min +4 2 h +3 23 h +2

[0142] Very good charging constancy over the entire activation period isfound. Application Examples for inkjet inks

Application Example 7

[0143] 10 parts of a finely ground 50% pigment preparation with thecolorant from Synthesis Example 1 (5 parts) in polyvinylchloride/polyvinyl acetate copolymer (5 parts), the homogeneous colorantdispersion being obtained by intensive kneading into the copolymer, areintroduced with stirring into a mixture of 80 parts of methyl isobutylketone and 10 parts of 1,2-propylene glycol, using a dissolver. Aninkjet ink having high transparency, lightfastness and good passagethrough the nozzles is obtained.

Application Example 8

[0144] 5 parts of colorant from Synthesis Example 1, in the form of a40% ultrafine aqueous pigment preparation, are admixed with stirring(paddle stirrer or dissolver) first with 75 parts of deionized water andthen with 6 parts of ®Mowilith DM 760 (acrylate dispersion), 2 parts ofethanol, 5 parts of 1,2-propylene glycol and 0.2 part of ®Mergal K7.This gives an inkjet ink having high transparency, high lightfastnessand good passage through the nozzles.

Application Example 9

[0145] 5 parts of colorant from Synthesis Example 1, in the form of a40% ultrafine aqueous pigment preparation, are admixed with stirringfirst with 80 parts of deionized water and then with 4 parts of®Luviskol K 30 (polyvinylpyrrolidone, BASF), 5 parts of 1,2-propyleneglycol and 0.2 parts of ®Mergal K7. This gives an inkjet ink having hightransparency, hight lightfastness and good passage through the nozzles.

[0146] Application Example of Powder Coating Materials

Application Example 10

[0147] 5 parts of the colorant from Synthesis Example 1 are incorporatedhomogeneously into 95 parts of a powder coating binder based on a TGICpolyester, e.g., ®Uralac P 5010 (DSM, Netherlands). In order todetermine the deposition rate, 30 g of the test powder coating materialare sprayed through a triboelectric gun at a defined pressure. Pressure[bar] Current [μA] Deposition rate [%] 3 1.8 78

1. The use of a copper phthalocyanine composition consisting essentiallyof a compound of the formula (I)

and of a compound of the formula (II)

as a colorant in electrophotographic toners and developers, powders andpowder coating materials, electret materials, inkjet inks, and colorfilters, wherein the compounds of the formulae (I) and (II) have aparticle morphology with an average length-to-width ratio of more than2.5:1.
 2. The use as claimed in claim 1, wherein the averagelength-to-width ratio is from 3:1 to 6:1.
 3. The use as claimed in claim1, wherin the quantitative ratio of the compound of the formula (I) tothe compound of the formula (II) is from 90:10 to 99:1% by weight. 4.The use as claimed in claim 1, wherein the compound of the formula (I)is C.I. Pigment Blue 15:3.
 5. The method as claimed in claim 1, whereinthe phthalocyanine composition is shaded with a further organic colorpigment, an inorganic pigment, or a dye.
 6. The method as claimed inclaim 1, wherein the phthalocyanine composition is used in combinationwith a charge control agent from the group of the triphenylmethanes;ammonium and immonium compounds; iminium compounds; fluorinated ammoniumand fluorinated immonium compounds; biscationic acid amides; polymericammonium compounds; diallylammonium compounds; aryl sulfide derivatives;phenol derivatives; phosphonium compounds and fluorinated phosphoniumcompounds; calix(n)arenes; cyclically linked oligosaccharides and theirderivatives, interpolyelectrolyte complexes; polyester salts; metalcomplex compounds, salicylate-nonmetal complexes, aluminum-azocomplexes, α-hydroxycarboxylic acid-metal and -nonmetal complexes; boroncomplexes of 1,2-dihydroxyaromatics, 1,2-dihydroxyaliphatics or2-hydroxy-1-carboxyaromatics; benzimidazolones; and azines, thiazines oroxazines.
 7. The use as claimed in claim 1 in liquid toners or powdertoners.
 8. An electrophotographic toner or developer comprising a tonerbinder, from 0.1 to 60% by weight of shaded or unshaded phthalocyaninecomposition, and from 0 to 20% by weight based in each case on theoverall weight of the toner or developer, of a charge control agent fromthe class of the triphenyimethanes, ammonium and immonium compounds;fluorinated ammonium and immonium compounds; biscationic acid amides;polymeric ammonium compounds; diallylammonium compounds; aryl sulfidederivatives; phenol derivatives; phosphonium compounds and fluorinatedphosphonium compounds; calix(n)arenes; cyclodextrins; polyester salts;metal complex compounds; cyclooligosaccharide-boron complexes,interpolyelectrolyte complexes; benzimidazolones; azines, thiazines oroxazines.
 9. An electrophotographic toner or developer comprising atoner binder, from 0.5 to 20% by weight of shaded or unshadedphthalocyanine composition, and from 0.1 to 5% by weight based in eachcase on the overall weight of the toner or developer, of a chargecontrol agent from the class of the triphenylmethanes, ammonium andimmonium compounds; fluorinated ammonium and immonium compounds;biscationic acid amides; polymeric ammonium compounds; diallylammoniumcompounds; aryl sulfide derivatives; phenol derivatives; phosphoniumcompounds and fluorinated phosphonium compounds; calix(n)arenes;cyclodextrins; polyester salts; metal complex compounds;cyclooligosaccharide-boron complexes, interpolyelectrolyte complexes;benzimidazolones; azines, thiazines or oxazines.
 10. A powder or powdercoating material comprising an acrylic resin or polyester resincontaining epoxy, carboxyl or hydroxyl groups, or a combination of suchresins, from 0.1 to 60% by weight of shaded or unshaded phthalocyaninecomposition, and from 0 to 20% by weight based in each case on theoverall weight of the powder or powder coating material, of a chargecontrol agent from the class of the triphenyi-methanes, ammonium andimmonium compounds; fluorinated ammonium and immonium compounds;biscationic acid amides; polymeric ammonium compounds; diallylammoniumcompounds; aryl sulfide derivatives; phenol derivatives phosphoniumcompounds and fluorinated phosphonium compounds; calix(n)arenes;cyclodextrins; polyester salts; metal complex compounds;cyclooligosaccharide-boron complexes, interpolyelectrolyte complexes;benzimidazolones; azines, thiazines or oxazines.
 11. A powder or powdercoating material comprising an acrylic resin or polyester resincontaining epoxy, carboxyl or hydroxyl groups, or a combination of suchresins, from 0.5 to 20% by weight of shaded or unshaded phthalocyaninecomposition, and from 0.1 to 5% by weight based in each case on theoverall weight of the powder or powder coating material, of a chargecontrol agent from the class of the triphenyl-methanes, ammonium andimmonium compounds; fluorinated ammonium and immonium compounds;biscationic acid amides; polymeric ammonium compounds; diallylammoniumcompounds; aryl sulfide derivatives; phenol derivatives; phosphoniumcompounds and fluorinated phosphonium compounds; calix(n)arenes;cyclodextrins; polyester salts; metal complex compounds;cyclooligosaccharide-boron complexes, interpolyelectrolyte complexes;benzimidazolones; azines, thiazines or oxazines.
 12. An inkjet inkcomprising from 0.5 to 15% by weight of a copper phthalocyaninecomposition as set forth in claim
 1. 13. An inkjet ink as claimed inclaim 10, which is a microemulsion ink, a solvent-based inkjet ink or ahot-melt inkjet ink.